Monoazodyestuffs



Patented July 20, 1937 PATENT FFlE MONOAZODYESTUFFS Otto Bayer,Lcverkusen-on-the-Rhine, Richard Fleischhauer,Frankfort-on-the-Main-Fechenheim, and Detlef Delis, Leverkusen-on-the-Rhine, Germany, assignors to General Aniline Works, Inc., New York, N.Y., a corporation of Delaware N Drawing.

rial No. 707,846. 1933 6 Claims.

relates to monoazodyestufis to those containing alkoXy- This inventionmore particularly acylamino groups.

These dyestuffs are obtained by combining a diam-component of thebenzene series with a coupling component of the pyrazolone ornaphthalene series, at least one of which components contains analkoxyacylamino group. They may also be prepared. by producingmonoazodyestuiis the components of which contain at least one primary orsecondary amino group and thereafter treating the products thus obtainedwith an alkyloxyacyl-halogenide or -anhydride.

As suitable diazo-components containing an alkoxyacylamino group may benamed those corresponding to the general formula:

alkyl0acyl NR-NH2 (wherein R means a benzene nucleus which may containsulfonic acid, methyl or methoxy groups and X means hydrogen, alkyl,aralkyl, cycloalkyl or aryl, i. e. for instance: l-methoxyacetylamino-4-aminobenzene, 1-methoxyacetylethylamino-4- aminobenzene,4-methoxyacetylamino-Z-aminol-methylbenzene,l-methoxyacetylcyclohexylamino 4 aminobenzene, 1ethoxyacetylaminolaminobenzene,1-ethoXyacety1amino-4-aminobenzene-3-sulfonic acid,l-c-methoxybutyrylamino- 3-aminobenzene,1-methoxyacetylbenzylaminoi-arninobenzene,l-methoxyacetylphenylaminol-aminobenzene, l-methyl-2-aminol-methoxy- 5methoxyacetylaminobenzene, 1 ,4 dimethoxy2-amino-5-methoxyacetylaminobenzene.

As suitable coupling components containing an alkoxyacylamino group maybe named those corresponding to the general formula:

6-sulfonic acid.

The new dyestuffs dye animal fibers as wool or Application January 22,1934, Se-

In Germany January 24,

silk clear yellow, orange-red, violet or brown shades. The shades aregenerally more yellowish than those of dyestuffs containing no alkoxygroup attached to their acyl group. Those of the dyestuffs containingthe alkoxyacylamino group attached to their coupling component show agood levelling power especially when compared with the correspondingdyestuffs containing an halogen-acylamino group instead of thealkoXy-acylamino group.

In order to further illustrate our invention the following examples aregiven, the parts being by weight; but We wish it, however, to beunderstood that our invention is not limited to the particularconditions nor specific products mentioned therein.

Example 1 20.7 parts of 1-methoxyacetyl-ethylamino-4- aminobenzene,prepared for example by acting with methoxyacetic acid anhydride onl-ethylaminol-nitrobenzene and subsequently reducing the obtainednitro-compound, are diazotized in the usual manner. The obtained diazosolution is allowed to run into a sodium carbonate solution of 35 partsof 2 (4-methoxyphenylamino)- 8-naphthol-6-sulfonic acid. The dyestufithus obtained forms after isolating and drying a dark water-solublepowder dyeing wool levelling yellowish brown shades.

By using instead of 2- (4'-methoxyphenylamino)-8-naphthol-6-sulfonicacid the equivalent amount of 2-phenylamino-8naphthol-S-sulfonic acid adyestuff of a like good levelling power but of a more reddish brownshade is obtained.

Similar brown dyestuffs are obtained by using as diazo-componentsl-methoxyacetylamino laminobenzene orl-methoxyacetylamino-4-aminobenzene-3-sulfonic acid orl-ethoxyacetylamino-4-aminobenzene-3-sulfonic acid,,B-methoxybutyrylamino-3-aminobenzene. 7

Example 2 9.2 parts of aniline are diazotized. The obtained diazosolution is allowed to run while cooling by means of ice into a sodiumcarbonate solution of 36 parts of l-methoxyacetylamino-S-naphtho1-4,6-disulfonic acid. The dyestuff thus obtained forms afterisolating and drying a red water-soluble powder dyeing Wool from an acidbath levelling bright red shades.

With 1 methoxyacetylamino-8-naphthol-3,6- disulionic acid a more bluishdyestuii is obtained.

The dyestufi described in the first paragraph may also be obtained byacting with methoxy acetic acid anhydride under suitable conditions onthe dyestuif obtained by combining diazotized aniline withl-amino-8-naphthol-4,6-disulfonic acid in the presence of-sodiumcarbonate.

The following table shows the shades of some further dyestuifs which areproduced according to the present process:-

Dyestuffs, containing the alkoryacylamino group in the diazo-componentDiazo-components coupling'components l-methoxyaiz e is y l s l isi i d Vl'methoxy' digiigidacetylaminoi-aminobenaqetylethy-l' hexylamino-4-aminobenzene-3-sulfonic ammo 4-aminobenzene acid enzene zene 1 (2-chloro 5- sulfophenyl) 3 methyl -5- Yellow Yell 0w Yellow Yellowpyrazolone. 2-naphthol-6,8-disulfonic acid Yellowish red Orange Orange 1-ac etylamino 8 naphthol 4,6- disulfonic Reddish violet Bluish acid. 1acetylamino -8 naphthol 3,6 disulfonic Reddish violet- Bluish red-Bluish red Bluish red Bluish red acid. 1-11aphthol-4-sulfonic acid RedRed 1-naphtho1-3,fi-disulfonic acid Red 2-amino-8-naphthol-6-sulfonicacid (cou- Bluish ted pled in an acid medium).2-(2-methoxy-phenylamino)-8-naphthol-6- Reddish brown Violet brown Brownsulfonic acid. l-toluene-sultamino-S -naphthol-3,6-disul- Reddish violetViolet red Violet red Bluish red fonic acld.

Dyestufls, containing the alkoaryacylamino group in the couplingcomponent Coupling components l-methoxyl-methoxy- 2-methoxy- 2-methoxy-Dlazo components acetylaminoacetylaminoacetylaminoacetylamino-B-naphthol- 8-naphthol- S-naphthol- 8-naphthol- 3,6-disulfonic4,6-disulionic 7-sulfonic fi-sulionic acld acid acid acid Aniline LOrange Yellowish red o-Toluidme- Bluish'red. Bluish red p-Toluidine.Bluish red- 2-chloro-4-amino-toluene Bluish red Bluish red-4-chloro-2-amino-toluene Bluish red- Bluish red Anthranilic acid Bluishred- Red p-Xylidine Bluish red- 2-chloro-5-amino benzoic acid. Bluishred- Bluish red 4-chloro-2-amino-anisol. Pink.-. Z-amino-diphenyletherPink- Bluish red. 4-amino-diphenylether Pink Bluish red Reddish or- Red7 ange. 4-amino;diphenylether-2-sulfonic acid Bluish red. Bluish red. Red dish or- Red e ange. -amino-diphenylether-fi-sulfonic acid PinkBluish red Reddish or- Red ange. l-ethylacetylamino-i-aminobeuzene RedRed 1-ethyl-benzoylamino-4-aminobenzene Bluish red. Bluish red.4-aminotoluene-B-sulianilide Bluish red. Anilinee3-sulfanilide Yellowishred o-Amino-diphenylsulfone Yellowish redl-ethyl-n1ethoxy-acetylaminoi-aminoben- Red;

zene. l-cyclohexyl-acetylamino-4-aminobenzene Red Oran e Red We claim:'

1. Monoazodyestufls of the group consisting of compounds of the generalformula:

2. Monoazodyestufis of the group consisting of compounds of the generalformula wherein R represents a coupling component of the naphthaleneseries, X represents a member selected from the group consisting ofhydrogen and alkyl and the radical NXCOCHz-O'alkyl is attached to eitherthe benzene nucleus or to the radical represented by R, and theirsubstituted compounds which contain a substituent selected from thegroup consisting of halogen, methyl, methoxy, acylamino and sulphonicacid group in the'benzene nucleus, when tl fi radical wherein Xrepresents a member selected from dyestufis dye animal fibers clearyellow, orange, red, violet to brown shades.

3. The monoazodyestuff of the formula:

which dyestuff dyes wool yellowish brown levelling shades.

4. The monoazodyestuff of the formula:

H2O HOzS cHr-CHz which dyestuff dyes wool bluish red levelling shades.

5. The monoazodyestuff of the formula:

OH NHCOCHaOCHs HaCHzC l i which dyestuff dyes wool bluish red levellingshades.

6. Monoazodyestuffs of the group consisting of 10 compounds of thegeneral formula:

o'r'ro BAYER.-

RICHARD FLEISCHHAUER). DETLEF DELFS.

